短肽自组装水凝胶的温和制备方法及免疫佐剂应用

短肽自组装水凝胶是一种新型的软物质材料,它由短肽通过自组装形成,具有生物活性和生物相容性高、易于设计与合成以及对外部刺激能快速响应等优点,它在生物医药、分析检测、组织工程等领域有很高的应用前景.本文主要总结了我们近年来在短肽自组装水凝胶温和制备方法研发方面的工作,同时介绍了短肽自组装水凝胶在疫苗佐剂方面的创新应用,并探讨了短肽自组装水凝胶研究领域的挑战及研究热点.     

用于软骨修复的水凝胶*

在软骨组织修复与再生中,水凝胶支架能够为细胞的增殖与分化提供更接近于天然软骨细胞外基质的微环境,是软骨组织修复的一种理想材料。本文介绍了近年发展起来的一些具有新结构和新性能的水凝胶,包括高强度水凝胶以及结构中包含功能蛋白和多肽的水凝胶。重点介绍了对温度、pH值及对生物分子产生响应的刺激响应型水凝胶和自组装水凝胶。具有α-螺旋结构和自组装水凝胶通过两个或多个卷曲螺旋结构聚集形成水凝胶,而通过多肽自组装形成的具有纤维结构的水凝胶在微观的结构上更接近软骨细胞外基质。此外,DNA的分子和序列也用来设计基于DNA的新型水凝胶。本文最后介绍了能在力学、生物学和可注射性等多方面更好地满足软骨修复需要的复合型水凝胶支架、干细胞与水凝胶的复合以及生长因子、基因和一些力学刺激对软骨再生的促进作用。     

DNA水凝胶在生物传感中的应用和发展

脱氧核糖核酸(DNA)是一种重要的生物分子,具有许多独特的性质如:信息传递、分子识别、可编辑等。DNA水凝胶同时具有DNA分子和水凝胶材料的优势,并且可以引入其他纳米材料获得多功能杂化水凝胶。相比于传统水凝胶,DNA水凝胶具有良好的特异识别能力以及可以按需设计的性质,从而被广泛应用于生物传感领域。本文围绕DNA水凝胶的合成、响应机制以及在传感领域的应用进行综述。按照不同的合成方法可分为线性DNA链缠绕水凝胶、枝状DNA自组装水凝胶、杂合DNA水凝胶。根据传感机制的不同又可以分为包埋封装法和非包埋封装法,包埋封装发法又分为:酶的包埋释放、抗原-抗体的包埋释放、纳米材料的包埋释放。本文总结了近几年DNA水凝胶在重金属离子检测、核酸检测、葡萄糖检测、蛋白质和代谢小分子检测,以及细胞检测等热门领域的研究情况,最后对其未来的发展进行了展望。     

天然高分子材料水凝胶的制备及其应用进展

水凝胶是一种由高分子聚合物构成的三维网络材料,用自然界中天然存在的高聚物及其衍生物材料构建水凝胶,具有生物相容性、环境敏感性高、生物可降解性和对环境无污染等优势。本文介绍了近几年天然高分子水凝胶材料在医药卫生、食品、农业和环保等领域的应用情况;并按材料来源的不同,分类综述了蛋白质、多肽类水凝胶,海藻多糖水凝胶,动物多糖水凝胶,植物多糖水凝胶,其改性和制备复合水凝胶的最新技术、功能特性以及应用领域;最后对天然高分子水凝胶制备的改进方向和重点应用领域进行了展望。     

光控水凝胶的构筑及在生物医药领域的应用

水凝胶由于具有优越的保水性、良好的生物相容性和可降解性,被认为是最接近人体组织的生物医用材料。通过构建环境敏感水凝胶可以高度拟合生物组织的微环境,实现其在组织工程与再生医学领域的应用。由于光具有非物理接触和时空分辨等优势,利用光调控技术可实现水凝胶微环境的精确构筑与调控。本文重点介绍了近年来光控水凝胶的构筑,以及在生物医学和材料领域的应用进展。     

多糖多肽水凝胶的增强研究

多糖多肽类天然水凝胶由于原料来源丰富、可生物降解以及良好的生物相容性,在生物医药领域具有巨大的应用潜力,然而其应用常常受到脆性高、力学强度差等缺陷的限制。本文综述了多糖多肽水凝胶的增强研究进展,重点探讨了共混增强、特殊拓扑结构增强、结晶增强和模仿合成材料凝胶增强等4种主要方法及其增强原理,并介绍了当前多糖多肽类水凝胶增强研究中取得的主要成果、面临的问题及其解决设想。     

水凝胶在人工眼角膜上的研究进展

理想的人工角膜植入材料要求物理化学性质稳定、生物相容性好、透光性高以及透气性好等,同时还应具有一定的折射能力,使得植入后能够达到矫正视力的目的。水凝胶因良好的生物相容性,及其对水溶性代谢产物如葡萄糖、营养物质、氧气等高的透过性,在眼科材料领域得到了非常广泛的应用。本文主要介绍了水凝胶材料在人工角膜上的研究进展,包括天然高分子水凝胶、合成高分子水凝胶、IPN互穿网络水凝胶以及高折射率有机-无机复合水凝胶。     

水凝胶流变学研究概况

水凝胶具有良好的生物相容性和生物可降解性,其结构呈三维网状结构,与细胞外基质相似,在药物释放和组织工程等领域具有广阔的应用前景,被广泛地用于生物制药、生物材料和医学等领域。流变学可以描述材料的流动特性和力学性能,水凝胶的粘弹响应对材料内部结构的变化也非常敏感,因此流变行为被视为研究水凝胶的一种重要方法。本文综述了流变学方法在水凝胶研究中的应用,介绍了水凝胶流变学的研究方法,讨论了影响水凝胶流变学特征的因素,并展望了水凝胶流变学的发展前景。     

两性离子水凝胶的制备及生物医学应用

两性离子水凝胶是一类含有两性离子聚合物的凝胶材料,其分子结构中的阴阳离子基团能与水分子紧密结合,形成致密的水合层。这种静电诱导水合作用使得两性离子水凝胶具有极低的生物黏附性,能有效抵抗非特异性蛋白、细胞、细菌等的黏附,具有极低的免疫原性。这些特性使得两性离子水凝胶在生物医用领域有广阔的应用前景。本综述首先介绍了两性离子水凝胶的结构及性质,然后概述了其分类和制备方法,并进一步总结了其在组织工程、药物载体、创伤敷料、生物传感器、医疗器械水凝胶涂层等生物医学领域中的应用。最后展望了两性离子水凝胶未来的发展方向。     

高分子水凝胶在医学领域的研究进展

高分子水凝胶是具有三维网络结构的一种新型材料,吸水溶胀后质地柔软,与生物体组织相似,生物相容性和生物可降解性良好,具有一定的力学性能,因此在医学领域具有重要的应用。本文对高分子水凝胶在医学领域的研究热点进行了归纳总结,并重点阐述了高分子水凝胶在药物输送、组织工程支架、伤口敷料和生物传感器等医学领域应用的最新研究进展,并对其未来发展趋势进行了展望。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.